Disperse azo dyes of the 2,6-diaminopyridine series

ABSTRACT

Disperse azo dyes of the 2,6-diaminopyridine series in which one of the amine groups in the 2-position or 6-position is acylated. The dyes give brilliant yellow to blue colorations of generally high fastness properties particularly on polyesters.

The invention relates to dyes of the formula (I): ##SPC1##

in which D is the radical of a diazo component; R is hydrogen,unsubstituted or substituted alkyl of one to seven carbon atoms orunsubstituted or substituted phenyl; Z is hydrogen, carbamoyl or cyano;one of the radicals X and Y is acyl and the other hydrogen orunsubstituted or substituted alkyl, cycloalkyl, aralkyl or phenyl.

Radicals D may be derived for example from amines of the benzene,benzothiazole, benzoisothiazole, thiazole, thiadiazole, thiophene,azobenzene or anthraquinone series and bear, particularly in the benzeneseries, preferably a second-order substituent, i.e. for example nitro,cyano, methylsulfonyl or carbomethoxy.

The following are examples of substituents for the radical D of thediazo component:

IN THE BENZENE SERIES: CHLORO, BROMO, NITRO, CYANO, TRIFLUOROMETHYL,METHYLSULFONYL, ETHYLSULFONYL, PHENYLSULFONYL, CARBOMETHOXY,CARBOBUTOXY, CARBO-β-METHOXYETHOXY, CARBO-β-HYDROXYETHOXY,UNSUBSTITUTED, N-monosubstituted or N-disubstituted carbamoyl orsulfonamide, methyl, ethyl, methoxy and ethoxy; examples ofN-substituents are: methyl, ethyl, propyl, butyl, β-hydroxyethyl,γ-hydroxyethyl, β-methoxyethyl, γ-methoxypropyl, γ-ethoxypropyl,pyrrolidide, piperidide and morpholide;

IN THE AZOBENZENE SERIES: CHLORO, BROMO, NITRO, CYANO, METHYL, ETHYL,METHOXY OR ETHOXY;

IN THE HETEROCYCLIC SERIES: CHLORO, BROMO, NITRO, CYANO, METHYL, ETHYL,PHENYL, METHOXY, ETHOXY, METHYLMERCAPTO, β-CARBOMETHOXYETHYLMERCAPTO,β-CARBETHOXYETHYLMERCAPTO, CARBOMETHOXY, CARBETHOXY, ACETYL,METHYLSULFONYL AND ETHYLSULFONYL.

Radical D may be derived specifically for example from the followingamines: aniline, o-toluidine, m-toluidine, p-toluidine, o-nitroaniline,p-nitroaniline, m-nitroaniline, o-cyanoaniline, m-cyanoaniline,p-cyanoaniline, 2,4-dicyanoaniline, o-chloroaniline, m-chloroaniline,p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline,2,4,6-tribromoaniline, 2-chloro-4-nitroaniline, 2-bromo-4-nitroaniline,2-cyano-4-nitroaniline, 2-methylsulfonyl-4-nitroaniline,2-methyl-4-nitroaniline, 2-methoxy-4-nitroaniline,4-chloro-2-nitroaniline, 4-methyl-2-nitroaniline, 4-methoxy-2-nitroaniline, 1-amino-2-trifluoromethyl-4-chlorobenzene,2-chloro-5-aminobenzonitrile, 2-amino-5-chlorobenzonitrile,1-amino-2-nitrobenzene-4-sulfonic acid n-butylamide orβ-methoxyethylamide, 2,4-dinitroaniline, 2,4-dinitro-6-chloroaniline,2,4-dinitro-6-bromoaniline, 2,4-dinitro-6-cyanoaniline,1-amino-2,4-dinitrobenzene-6-methylsulfone, 2,6-dichloro-4-nitroaniline,2,6-dibromo-4-nitroaniline, 2-chloro-6-bromo-4-nitroaniline,2,6-dicyano-4-nitroaniline, 2-cyano-4-nitro-6-chloroaniline,2-cyano-4-nitro-6-bromoaniline, 1-aminobenzene-4-methylsulfone,1-amino-2,6-dibromobenzene-4-methylsulfone,1-amino-2,6-dichlorobenzene-4-methylsulfone,1-amino-2,4-dinitrobenzene-6-carboxylic acid methyl ester orβ-methoxyethyl ester, propyl, 3,5-dichloroanthranilate, β-methoxyethyl,3,5-dibromoanthranilate, N-acetyl-p-phenylenediamine,4-aminoacetophenone, 4-aminobenzophenone, 2-aminobenzophenone,2-aminodiphenylsulfone, 4-aminodiphenylsulfone, the methyl, ethyl,propyl, butyl, isobutyl, β-methoxyethyl, β-ethoxyethyl, methyldiglycol,ethyldiglycol, methyltriglycol, ethyltriglycol, β-hydroxyethyl,β-acetoxyethyl, β-(β'-hydroxyethoxy)ethyl, β-hydroxypropyl,γ-hydroxypropyl, ω-hydroxybutyl, and ω-hydroxyhexyl ester of2-aminobenzoic, 3-aminobenzoic and 4-aminobenzoic acid, the methyl,isobutyl, methyldiglycol, β-methoxyethyl, β-butoxyethyl andβ-acetoxyethyl ester of 5-nitroanthranilic acid, the dimethyl, diethyl,dipropyl and dibutyl ester of 3-aminophthalic acid, 4-aminophthalicacid, 5-aminoisophthalic acid and aminoterephthalic acid, the amide,methylamide, propylamide, butylamide, isobutylamide, cyclohexylamide,β-ethylhexylamide, γ-methoxypropylamide and γ-ethoxypropylamide of3-aminobenzoic and 4-aminobenzoic acid, the dimethylamide diethylamide,pyrrolidide, morpholide and N-methyl-N-β-hydroxyethylamide of2-aminobenzoic, 3-aminobenzoic and 4-aminobenzoic acid, the diamide of5-amineisophthalic acid, the bis-γ-methoxypropylamide of5-aminoisophthalic acid, the bis-diethylamide of aminoterephthalic acid,3-aminophthalimide, 4-aminophthalimide, the β-hydroxyethylamide andγ-hydroxypropylamide of 3-aminophthalic and 4-aminophthalic acid, theβ-hydroxyethylamide of 3-amino-6-nitrophthalic acid, the dimethylamide,diethylamide, pyrrolidide and morpholide of 3-aminobenzene sulfonic and4-aminobenzenesulfonic acid, the 2'-aminophenyl, 3'-aminophenyl and4'-aminophenyl ester of methylsulfonic acid, the 2'-aminophenyl,3'-amino phenyl and 4'-aminophenyl ester of ethylsulfonic acid, the2'-aminophenyl, 3'-aminophenyl and 4'-aminophenyl ester of butylsulfonicacid, the 2'-aminophenyl, 3'-aminophenyl and 4'-aminophenyl ester ofbenzenesulfonic acid, 2-aminoanthraquinone,1-amino-4-chloroanthraquinone, 3-aminodiphenyl oxide, 4-aminodiphenyloxide, 2-aminobenzothiazole, 2-amino-6-carboxylic acid methyl esterbenzothiazole, 2-amino-6-methylsulfonylbenzothiazole,2-amino-6-cyanobenzothiazole, 2-amino-6-nitrobenzothiazole,5,6-dichloro-2-aminobenzothiazole, 6,7-dichloro-2-aminobenzothiazole,4-amino-5-bromo-7-nitro-1,2-benzoisothiazole,3-amino-5-nitro-2,1-benzoisothiazole,3-amino-5-nitro-7-bromo-2,1-benzoisothiazole, 2-aminothiazole,2-amino-5-nitrothiazole, the ethyl ester of2-amino-4-methylthiazole-5-carboxylic acid,2-amino-4-methyl-5-acetylthiazole,2-amino-3-cyano-4-methylthiophene-5-carboxylic ester,2-phenyl-5-amino-1,3,4-thiadiazole,3-methylmercapto-5-amino-1,2,4-thiadiazole,3-β-carbomethoxyethylmercapto-5-amino-1,2,4-thiadiazole and3-β-carbomethoxyethylmercapto-5-amino-1,2,4-thiadiazole.

Examples of suitable diazo components of the aminoazobenzene seies are:4-aminoazobenzene, 2',3'-dimethyl-4-aminoazobenzene,3',2-dimethyl-4-aminoazobenzene, 2,5-dimethyl-4-aminoazobene,2-methyl-5-methoxy-4-aminoazobenzene,2-methyl-4',5-dimethoxy-4-aminoazobenzene,4'-chloro-2-methyl-5-methoxy-4-aminoazobenzene,4'-nitro-2-methyl-5-methoxy-4-aminoazobenzen,4'-chloro-2-methyl-4-aminoazobenzene, 2,5-dimethoxy-4-aminoazobenzene,4'-chloro-2,5-dimethoxy-4-aminoazobenzene,4'-nitro-2,5-dimethoxy-4-aminoazobenzene,4'-chloro-2,5-dimethyl-4-aminoazobenzene,4'-methoxy-2,5-dimethyl-4-aminoazobenzene, 4'-nitro-4-aminoazobenzene,3,5-dibromo-4-aminoazobenzene, 2,3'-dichloro-4-aminoazobenzene,3-methoxy-4-aminoazobenzene, and 4'-hydroxy-2'-methyl-4-aminoazobenzene.

Examples of radicals R (apart from hydrogen) are: ethyl, n-propyl,isopropyl, butyl, pentyl, α-ethylpentyl, phenyl, methylphenyl and,preferably, methyl.

Examples of acyl radicals X or Y are: alkanoyl of one to ten carbonatoms which may be substituted by hydroxy, alkoxy, cyano, chloro,acetyl, phenyl or phenoxy; benzoyl which may be substituted by chloro,methyl or methoxy, and the radicals of the formulae: --SO₂ N--CH₃,--CONH₂, --CO--CH=CH--C₆ H₅, --COO--alkyl, --SO₂ alkyl, --SO₂ --aryl,--CONH--alkyl or --CONH--aryl.

Specific aexamples of acyl radicals are as follows: formyl, acetyl,propionyl, butyryl, hexanoyl, β-ethylhexanoyl, β-cyanoacetyl,β-chloracetyl, β-methoxyacetyl, β-phenoxyacetyl, β-phenylacetyl orβ-acetylacetyl and the radicals of the formulae: COOCH₃, COOC₂ H₅, COOC₃H₇. COOC₄ H₉, SO₂ CH₃, SO₂ C₂ H₅, SO₂ C₄ H₉, SO₂ C₆ H₅, ##SPC2##

Conhch₃, conhc₄ h₉ or CONHC₆ H₅.

The following substituents are other examples for X and Y (in additionto hydrogen and acyl radicals): alkyl of one to six carbon atoms, alkylsubstituted by hydroxy, cyano, alkoxy of one to eight carbon atoms,phenoxy, phenoxyethoxy or benzyloxy, cyclohexyl, benzyl, phenylethyl,phenylhydroxyethyl, phenylpropyl, phenylbutyl, phenyl substituted bychloro, methyl, methoxy or ethoxy, polyalkoxyalkyl,hydroxypolyalkoxyalkyl, alkanoyloxyalkyl or alkoxycarbonylalkyl.

Examples of individual radicals X and Y are: the alkyl radicals methyl,ethyl, propyl or butyl; the hydroxyalkyl radicals β-hydroxyethyl,β-hydroxypropyl, γ-hydroxypropyl, ω-hydroxyhexyl, and the radicals ofthe formulae --CH₂ --CH₂ --O--CH₂ --CH₂ --OH, --CH₂ --CH₂ --CH₂ --O--CH₂--CH₂ --CH₂ --CH₂ --OH, --(CH₂)₃ --O--(CH₂)₆ --OH, --(CH₂)₃ --O--(CH₂)₂--O--CH₃, --(CH₂)₃ --O--(CH₂)₂ --O(CH₂)₂ --OCH₃, --(CH₂)₃ --O--(CH₂)₂--O--C₆ H₅, --(CH₂)₃ --O--CH₂ --C₆ H₅, ##EQU1## --CH₂ --CH--C₆ H₅,##EQU2## ##SPC3## --CH₂ --CH₂ --OCH₃, --(CH₂)₃ --O--C₂ H₅, --(CH₂)₃--O--(CH₃)₂, C₆ H₅, and the acyloxyalkyl radicals of the formulae: --CH₂--CH₂ --O--acyl, --(CH₂)₃ --O--acyl, ##EQU3## --(CH₂)₆ --O--acyl,--(CH₂)₂ --O--(CH₂)₂ --O--acyl, --(CH₂)₃ --O--(CH₂)₄ --O--acyl ##EQU4##wherein acyl may be for example --COH or --COCH₃.

The dyes of the formula (I) may be prepared by reacting an amine of theformula (II): D--NH₂ (II) with a coupling component of the formula(III): ##SPC4##

where D, R, X, Y and Z have the above meanings.

Diazotization of the amines may be carried out by a conventional method.Coupling is also carried out conventionally in an aqueous medium, withor without the addition of solvents, in a weakly to strongly acidreaction.

If dyes according to the invention having the formula (I) contain anester group in the radical X or Y, the production of compounds of theformula (I) may be carried out in principle according to the saidprocess if the ester grozp is already contained in the couplingcomponent. In some cases, however, it is expedient to carry out firstcoupling and then esterification. Free acids, their anhydrides,chlorides or esters are suitable for esterification, and inert diluentsfor solvents such as monochlorobenzene, dichlorobenzene,trichlorobenzene, tetrahydrofuran, dioxane, dimethylformamide,nitrobenzene, N-methylpyrrolidone and pyridine may conveniently beadded.

In esterification with free acids it may be advantageous to addinorganic or organic catalysts, for example hydrogen chloride orp-toluenesulfonic acid and to allow the water formed to escape from thereaction mixture by evaporation. When acid anhydrides or acid chloridesare used for esterification the corresponding acids may in special casesbe used as the solvent. Thus the reaction with acetic anhydride may becarried out in glacial acetic acid. When using acid chlorides asesterification agents it is advantageous to add to the reaction mixturean acid-binding agent for example sodium carbonate, sodium acetate,magnesium oxide and pyridine. Examples of specific esterification agentsare: formic acid, acetic acid, chloroacetic acid and the esters,anhydrides or chlorides of these acids, and ethyl chloroformate,diketene, phenyl isocyanate and methyl isocyanate.

The N-acyl group X or Y is introduced by a conventional method, forexample by reaction of the coupling components of the formula (III),with X and/or Y being hydrogen, or of the dyes of the formula (I), withY being hydrogen, with, for example, formic acid, an acid anhydride, anacid chloride, ketene, diketene, an isocyanate, an alkylsulfonylchloride or an arylsulfonyl chloride. Details of the reactions will befound in the Examples.

Of particular industrial value are dyes and dye mixtures of the formula(Ia): ##SPC5##

where A is nitro, cyano, chloro, bromo, carbomethoxy, carbethoxy,β-methoxycarbethoxy, methylsulfonyl, ethylsulfonyl, methyl, methoxy andphenazo; A¹ is hydrogen, nitro, chloro, bromo, cyano, methyl methoxy,carbomethoxy, carbethoxy, methylsulfonyl and ehtylsulfonyl; A² ishydrogen, chloro, bromo, cyano, methyl, methoxy, carbomethoxy andcarbethoxy; and one of the radicals X¹ and Y¹ denotes formyl, alkanoylof one to three carbon atoms, benzoyl, alkylsulfonyl of one to fourcarbon atoms, phenylsulfonyl or tolylsulfonyl and the other radical ishydrogen or a radical containing a hydroxyl group which may beesterified by formyl.

Examples of preferred radicals containing hydroxyl groups are: --(CH₂)₃--O--(CH₂)₄ --OH; --(CH₂)₂ --O--(CH₂)₂ --OH, ##EQU5## --CH₂ --CH₂ --CH₂--OH, and --CH₂ --CH₂ --OH.

The corresponding dyes which contain (as diazo components) benzothiazole(which may be substituted by nitro, chloro, bromo, cyano, methyl,methylmercapto, β-carbomethoxyethylmercapto, β-carbethoxyethylmercapto,carbomethoxy, carbethoxy or acetyl, benzoisothiazole, thiazole,thiadiazole or thiophene are also particularly valuable.

Specific particularly valuable diazo components include the following:4-nitroaniline, 2-chloro-4-nitroaniline, 2-bromo-4-nitroaniline,2-cyano-4-nitroaniline, 2-methoxy-4-nitroaniline,2-amino-5-nitrophenylsulfonyl dimethylamide,2-amino-5-nitrophenylsulfonyl butylamide, 2-amino-5-nitrophenylsulfonylβ-methoxyethylamide, 2-aminobenzonitrile, 3-chloro-4-aminobenzonitrile,2-chloro-5-amino-benzonitrile, 2-amino-5-chlorobenzonitrile,3,5-dichloro-2-aminobenzonitrile, 1-amino-2,4-dicyanobenzene,1-amino-2,4-dicyano-6-chlorobenzene,2-chloro-4-amino-5-nitrobenzonitrile,2-amino-3-chloro-5-nitrobenzonitrile,2-amino-3-bromo-5-nitrobenzonitrile, 2,6-dicyano-4-nitroaniline,2,5-dichloro-4-nitroaniline, 2,6-dichloro-4-nitroaniline,2,6-dibromo-4-nitroaniline, 2-chloro-6-bromo-4-nitroaniline,2,4-dinitroaniline, 2,4-dinitro-6-chloroaniline,2,4-dinitro-6-bromoaniline, 2-amino-3,5-dinitrobenzonitrile,1-amino-4-nitrobenzene-2-methylsulfone,1-amino-4-nitrobenzene-2-ethylsulfone, 4-methylsulfonylaniline,1-amino-2-chlorobenzene-4-methylsulfone,1-amino-2,6-dibromobenzene-4-methylsulfone,1-amino-2,6-dichlorobenzene-4-methylsulfone, 2-aminobenzoic acid esters,4-aminobenzoic acid esters, 2-amino-5-nitrobenzoic acid esters,2-amino-3-chloro-5-nitrobenzoic acid esters, 2-amino-3,5-dichlorobenzoicacid esters, 2-amino-3,5-dibromobenzoic acid esters,methyl-2-amino-3,5-dinitrobenzoate, β-methoxyethyl2-amino-3,5-dinitrobenzoate, diethyl 2-aminoterephthalate,4-aminoanzobenzene, 2,3'-dimethyl-4-aminoazobenzene,2',3-dimethyl-4-aminoazobenzene, 2,5-dimethyl-4-aminoazobenzene, and3,5-dibromo-4-aminoazobenzene.

Particularly valuable heterocyclic diazo components include thefollowing: 2-amino-5-nitrothiazole, 2-amino-4-methyl-5-nitrothiazole,2-amino-4-methylthiazole-5-carboxylic ethyl ester,2-amino-5-phenyl-1,3,4-thiadiazole, 3-phenyl-5-amino-1,2,4-thiadiazole,3-methylmercapto-5-amino-1,2,4-thiadiazole,3-β-carbomethoxyethylmercapto-5-amino-1,2,4-thiadiazole,3-β-carbethoxyethylmercapto-5-amino-1,2,4-thiadiazole,2-amino-6-cyanobenzothiazole, 2-amino-6-carboxylic acid methyl esterbenzothiazole, 2-amino-6-nitrobenzothiazole,2-amino-3-cyano-4-methylthiophene-5-carboxylic esters,3-amino-5-nitro-2,1-benzoisothiazole,3-amino-5-nitro-7-chloro-2,1-benzoisothiazole,3-amino-5-nitro-7-bromo-2,1-benzoisothiazole,4-amino-7-nitro-1,2-benzoisothiazole,4-amino-5-bromo-1,2-benzoisothiazole,4-amino-5-bromo-7-nitro-1,2-benzoisothiazole,4-amino-5-cyano-7-nitro-1,2-benzoisothiazole,4-amino-5-chloro-7-nitro-1,2-benzoisothiazole.

The new dyes are yellow to blue and are suitable for dyeing textilematerial of acrylonitrile polymers, synthetic polyamides, celluloseesters such as secondary acetate or triacetate rayon, and particularlysynthetic linear polyesters such as polyethylene glycol terephthalate orpolymers having a similar chemical structure.

The dyes are also suitable for dyeing in organic solvents, such asperchloroethylene, and for transfer printing, provided they sublime attemperatures of from 160° to 240° C. They are however particularlyapplied from aqueous dispersion and according to the thermosol method.Dyeings are obtained which are distinguished by high tinctorial strengthand outstanding fastness properties.

The following examples, in which the parts and percentages are by weightunless otherwise specified, illustrate the invention.

EXAMPLE 1 a. Production of the coupling component:

100 parts by volume of glacial acetic acid is added to 81 parts of thereaction product of 2,6-dichloro-3-cyano-4-methylpyridine first with theamine of the formula H₂ N--(CH₃)₃ --O--(CH₂)₄ --OH and then with amonia;while stirring, 30 parts of methanesulfonyl chloride is added. The wholeis stirred for two hours at ambient temperature, about 80 parts byvolume of acetic acid is distilled off at subatmospheric pressure andthe residue is diluted with 500 parts of water and 35 parts of 50%caustic soda solution. The oil which separates is extracted with ethylacetate. After the extractant has been evaporated about 93 parts of abrown oil is obtained of the probable formula: ##SPC6##

b. Diazotization and coupling:

7.8 parts of 2-amino-3-chloro-5-nitrobenzonitrile is introduced at 0° to4° C in portions into a mixture of 40 parts of 96% sulfuric acid and 13parts of 23% nitroxylsulfonic acid. The whole is stirred for four hoursat 0° to 4° C and the diazonium salt mixture is then added in portionsto a solution, cooled to 0° C, of 14.3 parts of the abovementionedcoupling component in 1,500 parts of water and 11 parts of concentratedhydrochloric acid. Sodium acetate and ice are then added to the couplingmixture so that the pH is kept at 2 and the temperature does not riseabove 0° C. After coupling has been completed the mixture is heated atfrom 50° to 80° C, suction filtered and washed with water. After dryingabout 21 parts of a dark red powder is obtained having the probableformula: ##SPC7##

The powder dissolves is dimethylformamide to give a ruby color and dyespolyethylene glycol terephthalate fabric (by the high temperature andcarrier dyeing methods) full bluish red hues of excellent fastnessproperties.

EXAMPLE 2

6 parts of the dye of the formula: ##SPC8##

is stirred with 75 parts by volume of acetic acid and 20 parts of aceticanhydride for 2 hours under reflux. About 50 parts of volume of aceticacid is then distilled off, if necessary, at subatmospheric and 400parts by volume of water is added to the residue. The precipitated dyeof the probable formula: ##SPC9## is suction filtered, washed with waterand dried. 6 parts of a red powder is obtained which dissolves indimethylformamide a dark red color and dyes polyethylene glycolterephthalate fabric full red hues having excellent fastness properties.

EXAMPLE 3

45 parts of the product of the formula: ##SPC10##

is dissolved in 100 parts by volume of acetic acid at 80° C; then 26parts of acetic anhydride is added and the mixture is stirred for 10hours at 80° to 110° C. About 60 parts by volume of glacial acetic acidis distilled off and the residue has added to it 500 parts by volume ofwater and then 50% caustic soda solution until the pH is from about 2 to4.5. After cooling, about 45 parts of a crystalline colorless powder isobtained having the probable formula: ##SPC11##

which melts at 120° C.

10.5 parts of this powder is dissolved in 100 parts by volume of glacialacetic acid and 15 parts by volume of hydrochloric acid, and then asmall amount of sulfamic acid and 2,000 parts of ice-water are added.The diazonium salt mixture of 7.8 parts of2-amino-3-chloro-5-nitrobenzonitrile, 40 parts of sulfuric acid and 13parts of 23% nitrosylsulfuric acid (as described in Example 1) isgradually added to this mixture at 0° C. The pH of the coupling mixtureis raised to 2 to 3 by adding sodium formate solution. After couplinghas been completed the mixture is heated to 80° C, filtered and theprecipitated dye of the probable formula: ##SPC12##

is washed with water and dried. A dark red powder is obtained whichdissolves in N-methylpyrrolidone to give a ruby color and dyespolyethylene glycol terephthalate fabric bluish red hues havingexcellent fastness properties by the high temperature and carrier dyeingmethods.

EXAMPLE 4

11.8 parts of the product of the formula: ##SPC13##

is dissolved in 30 parts by volume of anhydrous acetic acid then 7.7parts of benzoyl chloride and 5 parts of anhydrous sodium acetate areadded; the whole is stirred for from five to ten hours at 50° to 100° Cand diluted with 1,500 parts of water and 20 parts by volume of 30%hydrochloric acid. The mixture thus obtained is cooled to 0° C and thefollowing diazonium salt solution is gradually added: 9.2 parts of2,4-dinitroaniline is dissolved at 70° C in 40 parts of sulfuric acidand cooled to 10° to 15°. 15.8 parts of nitrosylsulfuric acid (23%) isthen dripped in. The whole is stirred for one hour at this temperatureand then this mixture is added to 125 parts of ice and 60 parts byvolume of water. Stirring is continued for another hour at 0° to 5° C,after which time the mixture is filtered and added to the solution ofthe coupling component.

While the coupling mixture is at 0° C coupling is rapidly ended byadding aqueous caustic soda solution until the pH has risen to 2.5.After coupling is over the mixture is heated to about 50° C, suctionfiltered and the precipitated dye of the probable formula: ##SPC14##

is washed with hot water until it is salt-free. About 25 parts of a darkbrown powder is obtained which dissolves in dimethylformamide to give areddish violet color and dyes polyethylene glycol terephthalate fabricfull ruby red hues by the carrier and high temperature methods; thedyeings have very good fastness properties.

EXAMPLE 5

11.8 parts of 2-aminobenzonitrile is dissolved at room temperature in300 parts by volume of water and 40 party by volume of 30% hydrochloricacid. 300 parts of ice and 31 parts by volume of 23% sodium nitritesolution is then added, and the whole is stirred for 2 hours at 0° to 5°C and filtered. Any excess of nitrous acid present is destroyed asusual. The diazonium salt solution thus obtained is added in portions toa solution or suspension, cooled to 0° C, of 28.2 parts of the couplingcomponent of the formula: ##SPC15##

in a mixture of about 100 parts of dimethylformamide, 30 parts of 30%hydrochloric acid and 100 parts of water. To accelerate the couplingreaction the coupling mixture is brought to a pH of 2.5 to about 3.5 byadding 50% caustic soda solution. About 1,000 parts by volume ofice-water is added during coupling to enable the mixture to be stirredmore easily.

The precipitated dye of the formula: ##SPC16##

is suction filtered, washed with water and dried. About 36 parts of ayellow powder is obtained which dissolves in dimethylformamide to give ayellow color and dyes polyethylene terephthalate fabric full greenishyellow hues fast to light.

EXAMPLE 6

7 parts of the dye of the formula: ##SPC17##

is stirred for six hours at 100° C with 60 parts by volume of anhydrousacetic acid and 4 parts of diketene; another 4 parts of diketene is thenadded and the whole is stirred for another 6 hours at 100° C. About 30parts by volume of acetic acid is distilled off. The dye of the formula:##SPC18##

is isolated conventionally. About 7 parts of a yellowish brown powder isobtained which dissolves in dimethylformamide to give a dark yellowcolor and dyes polyethylene glycol terephthalate fabric golden yellowhues having very good fastness properties by the carrier and hightemperature dyeing methods (130° C).

EXAMPLE 7

At 0° to 4° C and while stirring well, 49 parts of2-amino-5-nitrobenzonitrile is added in portions to a mixture of 240parts of concentrated sulfuric acid and 98 parts of 23% nitrosylsulfuricacid. The mixture is stirred for from 4 to 5 hours at 0° to 4° C and isthen added in portions to a suspension of 123 parts of the couplingcomponent of the formula: ##SPC19##

acid and 150 parts of water.

Ice and sodium formate solution are added during coupling so that the pHof the mixture is from 2 to 0 and the temperature is about 0° C. Aftercoupling is over the dye of the formula: ##SPC20##

is isolated by a conventional method. A dark red powder is obtainedwhich dyes polyester fibers very easily.

The hues given in the Tables refer to dyeings with the dyes onpolyethylene glycol terephthalate:

TABLE 1 ##SPC21##No. R X YHue__________________________________________________________________________8CH₃ --COCH₃ --(CH₂)₃ --O--(CH₂)₄ --OH scarlet9 H " " "10 C₃ H₇ " " "11CH₃ --COC₂ H₅ " "12 " --COCH₂ CH₂ OCH₃ " "13 " --COCH₃ --CH₂ --CH₂ --C₆H₅ "14 " " --CH₂ --CH--C₆ H₅ " | OH15 " " --(CH₂)₃ --O--(CH₂)₂ --OC₆ H₅"16 " " --(CH₂)₃ --O--CH₂ --C₆ H₅ "17 " --COCH₂ --O--C₆ H₅ --CH₂ --CH₂O--CH₃ "18 C₆ H₅ --COCH₃ --CH₂ --CH₂ --O--CH₂ --CH₂ "H19 CH₃ --CH₂ --CH₂--C₆ H₅ --COCH₂ --COCH₃ yellowish red20 " " --COCH₃ scarlet21 " --(CH₂)₃--O--(CH₂)₄ --OH " "22 H --SO₂ CH₃ --(CH₂)₃ --O--(CH₂)₄ --OH "23 CH₃--CO₂ C₆ H₅ --(CH₂)₂ --O--(CH₂)₂ --OH "24 " --SO₂ CH₃ --CH₂ --CH--C₆ H₅" | OH25 " " --CH₂ --CH₂ --C₆ H₅ "26 " --SO₂ --C₂ H₅ --CH.sub. 2--CH--C₆ H₅ " | OH27 " --SO₂ --CH₃ --(CH₂)₃ --O--(CH₂)₂ --OC₆ H₅ "28 "--CH₂ --CH₂ --C₆ H₅ --SO₂ CH₃ "29 " --(CH₂)₃ --O--(CH₂)₂ --OC₆ H₅ ""__________________________________________________________________________TABLE 2 ##SPC22##

    No.                                                                              R     X               Y               Hue                                  __________________________________________________________________________    30 --CH.sub.3                                                                          --COCH.sub.3    --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4                                                      bluish red                           31 --CH.sub.3                                                                          --COC.sub.2 H.sub.5                                                                           "               "                                    32 "     "               --(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2                                                      "-OH                                 33 --C.sub.3 H.sub.7 (n)                                                               --COCH.sub.3    --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4                                                      "-OH                                 34 --CH.sub.3                                                                          --CO.sub.2 CH.sub.3                                                                           --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       "                                    35 "     --COCH.sub.3    "               "                                    36 "     "               --CH.sub.2 --CH--C.sub.6 H.sub.5                                                              "                                                             |                                                                    OH                                                   37 "     "               --(CH.sub.2).sub.3 --O--CH.sub.2 --C.sub.6                                    H.sub.5         "                                    38 "     "               --(CH.sub.2).sub.3 --O--(CH.sub. 2).sub.2                                     --O--C.sub.6 H.sub.5                                                                          "                                    39 "     --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       --COCH.sub.3    "                                    40 "     --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub.6 H.sub.5                                 "               "                                    41 "     --CO--C.sub.6 H.sub.5                                                                         --(CH.sub.2).sub.2 --O--(OH.sub.2).sub.2                                                      "-OH                                 42 "     --COCH.sub.2 --O--C.sub.6 H.sub.5                                                             --(CH.sub.2 --CH.sub.2 --O--CH.sub.3                                                          "                                    43 "     "               --CH.sub.2 --CH.sub.2 --OH                                                                    "                                    44 "     --CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                           --SO.sub.2 CH.sub.3                                                                           "                                    45 "     --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub.6 H.sub.5                                 "               "                                    46 "     --SO.sub.2 CH.sub.3                                                                           --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4                                                      "-OH                                 47 "     --SO.sub.2 C.sub.2 H.sub.5                                                                    "               "                                    48 "     "               --(CH.sub.2).sub.2 O--(CH.sub.2).sub.2 --OH                                                   "                                    49 "     --SO.sub.2 CH.sub.3                                                                           --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       "                                    50 "     "               --CH.sub.2 --CH--C.sub.6 H.sub.5                                                              "                                                             |                                                                    CH.sub.3                                             51 "     --SO.sub.2 --C.sub.6 H.sub.5                                                                  --(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2                                                      "-OH                                 52 --C.sub.3 H.sub.7 (i)                                                               --SO.sub.2 CH.sub.3                                                                           --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4                                                      "-OH                                 53 --CH.sub.3                                                                          --SO.sub.2 CH.sub.3                                                                           --C.sub.6 H.sub.5                                                                             "                                    54 "     --COCH.sub.3    "               "                                    55 "     --CONH--C.sub.4 H.sub.9 (n)                                                                   --CH.sub.2 --CH.sub.2 --CH.sub.2 --OCH.sub.3                                                  "                                    __________________________________________________________________________

TABLE 3 ##SPC23##

    No.                                                                              R     X         Y               Hue                                        __________________________________________________________________________    56 --CH.sub.3                                                                          --COCH.sub.3                                                                            --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4 --OH                                                 red                                        57 "     --COC.sub.2 H.sub.5                                                                     "               "                                          58 "     --COCH.sub.2 OC.sub.6 H.sub.5                                                           --CH.sub.2 --CH.sub.2 --CH.sub.2 --OH                                                         "                                          59 "     "         --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       "                                          60 "     --COCH.sub.3                                                                            --(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2 --O--C.sub.6                         H.sub.5         "                                          61 "     --CH.sub.2 --CH.sub.2 --OCH.sub.3                                                       --COCH.sub.2 --O--C.sub.6 H.sub.5                                                             ruby                                       62 --C.sub.2 H.sub.5                                                                   --COCH.sub.3                                                                            --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4 --OH                                                 bluish red                                 63 --C.sub.3 H.sub.7 (n)                                                               "         "               bluish red                                 64 --CH.sub.3                                                                          --SO.sub.2 CH.sub.3                                                                     "               red                                        65 "     --SO.sub.2 C.sub.6 H.sub.5                                                              --(CH.sub.2).sub.2 O--(CH.sub.2).sub.2 --OH                                                   "                                          66 --C.sub.2 H.sub.5                                                                   "         "               "                                          67 --C.sub.3 H.sub.7                                                                   --SO.sub.2 CH.sub.3                                                                     "               "                                          68 --H   "         --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4 --OH                                                 "                                          69 --CH.sub.3                                                                          "         --C.sub.6 H.sub.5                                                                             bluish red                                 70 "     "         --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       red                                        71 "     "         --CH.sub.2 --CH--C.sub.6 H.sub.5                                                              "                                                             |                                                                    OH                                                         72 "     "         --(CH.sub.2).sub.3 --O--CH.sub.2 --C.sub.6 H.sub.5                                            "                                          73 "     "         --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub.6                         H.sub.5         "                                          __________________________________________________________________________

TABLE 4 ##SPC24##

    No.                                                                              R     X              Y               Hue                                   __________________________________________________________________________    74 --CH.sub.3                                                                          --COCH.sub.3   --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4 OH                                                   bluish red                            75 --C.sub.2 H.sub.5                                                                   "              "               "                                     76 --C.sub.3 H.sub.7 (n)                                                               "              "               "                                     77 --H   "              "               "                                     78 --C.sub.6 H.sub.5                                                                   "              --(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2 --OH                                                 "                                     79 --H   --COC.sub.2 H.sub.5                                                                          --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4 --OH                                                 "                                     80 --CH.sub.3                                                                          "              "               "                                     81 --C.sub.2 H.sub.5                                                                   "              "               "                                     82 --CH.sub.3                                                                          --COCH.sub.2 OC.sub.6 H.sub.5                                                                --CH.sub.2 --CH.sub.2 --OH                                                                    "                                     83 "     "              --CH.sub.2 --CH.sub.2 --CH.sub.2 --OH                                                         "                                     84 "     "              -- CH.sub.2 --CH.sub.2 --O--CH.sub.3                                                          "                                     85 "     --COCH.sub.3   --C.sub.6 H.sub.5                                                                             ruby                                  86 "     --CO.sub.2 CH.sub.3                                                                          --C.sub.6 H.sub.5                                                                             ruby                                  87 "     --COCH.sub.3   --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       bluish red                            88 "     --COCH.sub.3   --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.su                            b.6 H.sub.5     "                                     89 "     --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                      --COCH.sub.3    "                                     90 "     "              --COOCH.sub.3   "                                     91 "     "              --COCH.sub.2 --COCH.sub.3                                                                     ruby                                  92 "     --CH.sub.2 --CH.sub.2 --CH.sub.2 --OCOCH.sub.3                                               --COCH.sub.3    bluish red                            93 "     --SO.sub.2 CH.sub.3            "                                     94 "     --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4 OCOCH.sub.3                                         --COCH.sub.3    "                                     95 "     --SO.sub.2 CH.sub.3                                                                          --(CH.sub.2).sub.3 --O--(CH.sub. 2).sub.4                                                     "-OH                                  96 --H   --SO.sub.2 C.sub.2 H.sub.5                                                                   "               "                                     97 --CH.sub.3                                                                          --SO.sub.2 C.sub.6 H.sub.5                                                                   --(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2 OH                                                   "                                     98 "     --SO.sub.2 CH.sub.3                                                                          --C.sub.6 H.sub.5                                                                             ruby                                  99 "     "              --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       bluish red                             100                                                                             "     "              --CH.sub.2 --CH--C.sub.6 H.sub.5                                                              "                                                             |                                                                    OH                                                     101                                                                             "     "              --(CH.sub.2).sub.3 --O--CH.sub.2 --C.sub.6                                    H.sub.5         "                                      102                                                                             "     "              --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.su                            b.6 H.sub.5     "                                      103                                                                             --H   "                              ruby                                   104                                                                             --CH.sub.3                                                                          "              --CH.sub.2 --CH.sub.2 --CH.sub.2 --OH                                                         bluish red                             105                                                                             "     "              -- CH.sub.2 --CH--CH.sub.3                                                                    "                                                             |                                                                    OH                                                     106                                                                             "     --CH.sub.2 --CH.sub.2 --OH                                                                   --SO.sub.2 CH.sub.3                                                                           "                                      107                                                                             "     --CH.sub.2 --CH.sub.2 --CH.sub.2 --OH                                                        "               "                                      108                                                                             "     --C.sub.2 H.sub.5                                                                            "               "                                      109                                                                             "     --C.sub.3 H.sub.7 (n)                                                                        "               "                                      110                                                                             "     --C.sub.4 H.sub.9 (n)                                                                        "               "                                      111                                                                             "     --CH.sub.2 --CH.sub.2 --CH.sub.2 --OCH.sub.3                                                 "               "                                      112                                                                             "     --(CH.sub.2).sub.3 --O--CH(CH.sub.3).sub.2                                                   "               "                                      113                                                                             "     --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                      "               "                                      114                                                                             "     --C.sub.6 H.sub.5                                                                            "               "                                     __________________________________________________________________________

TABLE 5 ##SPC25##

    No.                                                                              R     X               Y               Hue                                  __________________________________________________________________________    115                                                                              --H   --COCH.sub.3    --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4                                                      red orange                           116                                                                              --CH.sub.3                                                                          "               "               "                                    117                                                                              --H   --COC.sub.2 H.sub.5                                                                           "               "                                    118                                                                              "     --COCH.sub.3    --(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2 --OH        119                                                                              "     "               --CH.sub.2 --CH.sub.2 --CH.sub.2 --OH                                                         "                                    120                                                                              "     "               --(CH.sub.2).sub.3 --O--COCH.sub.3                                                            "                                    121                                                                              "     "               --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       "                                    122                                                                              --H   "                               scarlet                              123                                                                              "     "               --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2                                      --O--C.sub.6 H.sub.5                                                                          red orange                           124                                                                              "     "               --(CH.sub.2).sub.3 --O--CH.sub.2 --C.sub.6                                    H.sub.5         "                                    125                                                                              "     "               --CH.sub.2 --CH--C.sub.6 H.sub.5                                                              "                                                             |                                                                    OH                                                   126                                                                              --CH.sub.3                                                                          --CH.sub.2 --CH.sub.2 --CH.sub.2 --OCOCH.sub.3                                                --COCH.sub.3    orange                               127                                                                              "     --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       "               "                                    128                                                                              "     --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub.6 H.sub.5                                 "               "                                    129                                                                              "     --CH.sub.2 --CH.sub.2 --OCH.sub.3                                                             --COCH.sub.2 --O--C.sub.6 H.sub.5                                                             "                                    130                                                                              "     --C.sub.6 H.sub.5                                                                             --COCH.sub.2 COCH.sub.3                                                                       scarlet                              131                                                                              "     --C.sub.6 H.sub.5                                                                             --COCH.sub.3    "                                    132                                                                              --C.sub.2 H.sub.5                                                                   --COCH.sub.3    --C.sub.6 H.sub.5                                                                             "                                    133                                                                              --C.sub.3 H.sub.7 (n)                                                               --COCH.sub.3    --C.sub.6 H.sub.5                                                                             "                                    134                                                                              --CH.sub.3                                                                          --COC.sub.6 H.sub.5                                                                           --(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2                                                      "H                                   135                                                                              "     --COC.sub.6 H.sub.5                                                                           --CH.sub.2 --CH.sub.2 --CH.sub.2 OH                                                           "                                    136                                                                              "     --COCH=CH--C.sub.6 H.sub.5                                                                    --CH.sub.2 --CH.sub.2 OCH.sub.3                                                               orange                               137                                                                              "     --SO.sub.2 CH.sub.3                                                                           --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4                                                      red orange                           138                                                                              "     --SO.sub.2 C.sub.2 H.sub.5                                                                    --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4                                                      "-OH                                 139                                                                              "     --SO.sub.2 C.sub.6 H.sub.5                                                                    --(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2                                                      "-OH                                 140                                                                              "     --SO.sub.2 CH.sub.3                                                                           --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       "                                    141                                                                              "     "               --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2                                      --O--C.sub.6 H.sub.5                                                                          "                                    142                                                                              "     "               --CH.sub.2 --CH--C.sub.6 H.sub.5                                              |                                                                    OH                                                   143                                                                              --H   "               --CH.sub.2 --CH.sub.2 --C.sub.                                                                " H.sub.5                            144                                                                              --H   "               --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4 OH          145                                                                              --H   "               --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2                                      --O--C.sub.6 H.sub.5                                                                          "                                    146                                                                              --H   --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub.6 H.sub.5                                 --SO.sub.2 CH.sub.3                                                                           orange                               147                                                                              --CH.sub.3                                                                          "               "               "                                    148                                                                              --CH.sub.3                                                                          --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       "               "                                    149                                                                              --CH.sub.3                                                                          --C.sub.6 H.sub.5                                                                             "               red orange                           150                                                                              --CH.sub.3                                                                          --SO.sub.2 CH.sub.3                                                                           --C.sub.6 H.sub.5                                                                             "                                    __________________________________________________________________________

TABLE 6 ##SPC26##

    No.                                                                              R   X               Y               Hue                                    __________________________________________________________________________    151                                                                              --H --COCH.sub.3    (CH.sub.2).sub.3 --O--(CH.sub.2).sub.4 --OH                                                   orange                                 152                                                                              --CH.sub.3                                                                        "               "               "                                      153                                                                              "   "               --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4 --OCOCH.su                           b.3             "                                      154                                                                              "   "               --(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2 --OH                                                 "                                      155                                                                              "   "               --CH.sub.2 --CH.sub.2 --CH.sub.2 --OH                                                         "                                      156                                                                              "   --COCH.sub.2 --O--C.sub.6 H.sub.5                                                             --CH.sub.2 --CH.sub.2 --CH.sub.2 --OH                                                         "                                      157                                                                              "   "               --CH.sub.2 --CH.sub.2 --OH                                                                    "                                      158                                                                              "   --COCH.sub.3    --CH.sub.2 --CH.sub.2 --OH                                                                    "                                      159                                                                              "   "               --CH.sub.2 --C.sub.6 H.sub.5                                                                  "                                      160                                                                              "   "               --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       "                                      161                                                                              "   "               --CH.sub.2 --CH--C.sub.6 H.sub.5                                                              "                                                             |                                                                    OH                                                     162                                                                              "   "               --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub                           .6 H.sub.5      "                                      163                                                                              "   "               --COCH.sub.3    yellowish                                                                     orange                                 164                                                                              "   --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub.6 H.sub.5                                 --COCH.sub.3    "                                      165                                                                              "   --SO.sub.2 CH.sub.3                                                                           --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4 --OH                                                 orange                                 166                                                                              "   "               --(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2 --OH                                                 "                                      167                                                                              "   "               --(CH.sub.2).sub.3 --OH                                                                       "                                      168                                                                              "   "               --C.sub.6 H.sub.5                                                                             "                                      169                                                                              "   "                               "                                      170                                                                              "   "               --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       "                                      171                                                                              "   "               --CH.sub.2 --CH--C.sub.6 H.sub.5                                                              "                                                             |                                                                    OH                                                     172                                                                              "   "               --CH.sub.2 --CH--C.sub.6 H.sub.5                                                              "                                                             |                                                                    OH                                                     173                                                                              "   "               --CH.sub.2 --CH.sub.2 --CH--C.sub.6 H.sub.5                                                   "                                                             |                                                                    OH                                                     174                                                                              "   "               --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub                           .6 H.sub.5      "                                      175                                                                              "   --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub.6 H.sub.5                                 --SO.sub.2 CH.sub.3                                                                           yellowish                                                                     orange                                 176                                                                              "   --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       --SO.sub.2 CH.sub.3                                                                           "                                      __________________________________________________________________________

TABLE 7 ##SPC27##

    No.                                                                              R     X               Y               Hue                                  __________________________________________________________________________    177                                                                              --CH.sub.3                                                                          --COCH.sub.3    (CH.sub.2).sub.2 --O--(CH.sub.2).sub.2 --OH                                                   yellow                               178                                                                              "     "               --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4                                                      "-OH                                 179                                                                              "     "               --CH.sub.2 --CH.sub.2 --CH.sub.2 --OH                                                         "                                    180                                                                              "     "                               "                                    181                                                                              "     --CO.sub.2 CH.sub.3                                                                           "               "                                    182                                                                              "     --COCH.sub.3    CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                         "                                    183                                                                              "     --COCH.sub.3    --CH.sub.2 --CH--C.sub.6 H.sub.5                                                              "                                                             |                                                                    OH                                                   184                                                                              "     --COCH.sub.2    (CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub                             .6 H.sub.5      "                                    185                                                                              "     --COC.sub.6 H.sub.5                                                                           --(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2                                                      "-OH                                 186                                                                              "     --COCH.sub.2 --O--C.sub.6 H.sub.5                                                             --CH.sub.2 --CH.sub.2 --OH                                                                    "                                    187                                                                              "     "               --(CH.sub.2).sub.3 --OH                                                                       "                                    188                                                                              "     --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       --CO.sub.2 CH.sub.3                                                                           "                                    189                                                                              "     --SO.sub.2 CH.sub.3                                                                           --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4                                                      "-OH                                 190                                                                              --H   "               "               "                                    191                                                                              --CH.sub.3                                                                          "               "               "                                    192                                                                              --C.sub.3 H.sub.7 (n)                                                               "               "               "                                    193                                                                              --CH.sub.3                                                                          "               --(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2                                                      "-OH                                 194                                                                              "     --SO.sub.2 C.sub.6 H.sub.5                                                                    --(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2                                                      "-OH                                 195                                                                              "                     "               "                                    196                                                                              "     --SO.sub.2 CH.sub.3                                                                           --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2                                      --O--C.sub.6 H.sub.5                                                                          "                                    197                                                                              "     --SO.sub.2 CH.sub.3                                                                           --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       "                                    198                                                                              "     --SO.sub.2 CH.sub.3                                                                           --C.sub.6 H.sub.5                                                                             "                                    199                                                                              "     --C.sub.6 H.sub.5                                                                             --SO.sub.2 CH.sub.3                                                                           "                                    200                                                                              "     --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       --SO.sub.2 CH.sub.3                                                                           "                                    201                                                                              "     --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --C--C.sub.6 H.sub.5                                 --SO.sub.2 CH.sub.3                                                                           "                                    202                                                                              "     --CO--CH.sub.2 --CN                                                                           --CH.sub.2 --CH.sub.2 --OH                                                                    "                                    203                                                                              "     --SO.sub.2 CH.sub.3                                                                           --CH.sub.2 --CH.sub.2 --COOCH.sub.3                                                           "                                    204                                                                              "     --COCH=CH--C.sub.6 H.sub.5                                                                    --C.sub.2 H.sub.5                                                                             "                                    __________________________________________________________________________

TABLE 8 ##SPC28##

    No.                                                                              R   X         Y               Hue                                          __________________________________________________________________________    205                                                                              --CH.sub.3                                                                        --COCH.sub.3                                                                            --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4 --OH                                                 scarlet                                      206                                                                              "   --COCH.sub.3                                                                            --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4 --OH                                                 "                                            207                                                                              "   --COCH.sub.3                                                                            --CH.sub.2 --CH.sub.2 --CH.sub.2 --OH                                                         "                                            208                                                                              "   --COCH.sub.2 --O--C.sub.6 H.sub.5                                                       --CH.sub.2 --CH.sub.2 --OH                                                                    "                                            209                                                                              "   --SO.sub.2 CH.sub.3                                                                     --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       "                                            210                                                                              "   --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                 --COCH.sub.3    "                                            211                                                                              "   --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                 --SO.sub.2 CH.sub.3                                                                           "                                            212                                                                              "   --SO.sub.2 CH.sub.3                                                                     --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub.6                         H.sub.5         "                                            __________________________________________________________________________

TABLE 9 ##SPC29##

    No.                                                                              R   X               Y               Hue                                    __________________________________________________________________________    213                                                                              --CH.sub.3                                                                        --CHO           --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4 --OH                                                 bluish red                             214                                                                              --H --COCH.sub.3    "               "                                      215                                                                              --CH.sub.3                                                                        "               "               "                                      216                                                                              "   "               --(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2 --OH                                                 "                                      217                                                                              "   "               --CH.sub.2 --CH.sub.2 --CH.sub.2 --OH                                                         "                                      218                                                                              "   "               --CH.sub.2 --CH.sub.2 --CH.sub.2 --OCH.sub.3                                                  "                                      219                                                                              "   --COC.sub.6 H.sub.5                                                                           --(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2 --OH                                                 "                                      220                                                                              "   --COCH.sub.3    --CH.sub.2 --CH--C.sub.6 H.sub.5                                                              "                                                             |                                                                    OH                                                     221                                                                              "   "               --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       "                                      222                                                                              "   "               --C.sub.6 H.sub.5                                                                             reddish                                                                       violet                                 223                                                                              "   "               --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub                           .6 H.sub.5      bluish red                             224                                                                              "   --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       --CHO           "                                      225                                                                              "   --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       --COCH.sub.3    "                                      226                                                                              "   --SO.sub.2 CH.sub.3                                                                           --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       "                                      227                                                                              "   "               --CH.sub.2 --CH--C.sub.6 H.sub.5                                                              "                                                             |                                                                    OH                                                     228                                                                              "   "               --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4 --OH                                                 "                                      229                                                                              "   "               --(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2 --OH                                                 "                                      230                                                                              "   "               --CH.sub.2 --CH.sub.2 --CH.sub.2 --OH                                                         "                                      231                                                                              "   "               --CH.sub.2 --CH.sub.2 --OH                                                                    "                                      232                                                                              "   "               -- CH.sub.2 --CH.sub.2 --O--CH.sub.3                                                          "                                      233                                                                              "   --SO.sub.2 C.sub.6 H.sub.5                                                                    --(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2 --OH                                                 "                                      234                                                                              "   --SO.sub.2 CH.sub.3                                                                           --(CH.sub.2).sub.3 --O--CH.sub.2 --C.sub.6                                                    ".sub.5                                235                                                                              "   "               --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub                           .6 H.sub.5      "                                      236                                                                              "   "               --C.sub.6 H.sub.5                                                                             red violet                             237                                                                              "   --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       --SO.sub.2 CH.sub.3                                                                           bluish red                             238                                                                              "   --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub.6 H.sub.5                                 "               "                                      __________________________________________________________________________

TABLE 10 ##SPC30##

    No.                                                                              R   X               Y               Hue                                    __________________________________________________________________________    239                                                                              --CH.sub.3                                                                        --COCH.sub.3    --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4 --OH                                                 yellowish                                                                     red                                    240                                                                              "   --COCH.sub.3    --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.6 --OH                                                 "                                      241                                                                              "   --COC.sub.6 H.sub.5                                                                           --(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2 --OH                                                 "                                      242                                                                              "   --COCH.sub.3    --CH.sub.2 --CH.sub.2 --CH.sub.2 --OH                                                         "                                      243                                                                              "   --COCH.sub.3    --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub                           .6 H.sub.5      "                                      244                                                                              "   --CHO           --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       "                                      245                                                                              "   --COCH.sub.3    "               "                                      246                                                                              "   --SO.sub.2 CH.sub.3                                                                           "               "                                      247                                                                              "   "               --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4 --OH                                                 "                                      248                                                                              "   "               --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub                           .6 H.sub.5      "                                      249                                                                              "   "               --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       "                                      250                                                                              "   --CH.sub.2 --CH.sub.2 --C.sup.6 H.sup.5                                                       --CHO           "                                      251                                                                              "   "               --SO.sub.2 CH.sub.3                                                                           "                                      252                                                                              "   --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub.6 H.sub.5                                 --SO.sub.2 CH.sub.3                                                                           "                                      __________________________________________________________________________

TABLE 11

Coupling component: ##SPC31##

    No.         Diazo component    Hue                                            ______________________________________                                        253                        yellow                                             254                        greenish yellow                                    255                        scarlet                                            256                        orange                                             257                        bluish red                                         ______________________________________                                    

TABLE 12 ##SPC32##

    No.       Diazo component        Hue                                          ______________________________________                                        258                          yellow                                           259                          yellow                                           260                          orange                                           261                          scarlet                                          262                          bluish red                                       263                          bluish red                                       264                          yellowish orange                                 265                          bluish red                                       266                          yellow                                           267                          yellow                                           ______________________________________                                    

TABLE 13

Coupling component: ##SPC33##

    No.                                                                              Diazo component          Hue                                               __________________________________________________________________________    269                         yellow                                            270                         yellow                                            271                         yellow                                            272                         bluish red                                        273                         yellow                                            274                         scarlet                                           275                         orange                                            276                         orange                                            __________________________________________________________________________

TABLE 14

Coupling component: ##SPC34##

    No.    Diazo component      Hue                                               ______________________________________                                        277                         red                                               278                         reddish violet                                    279                         reddish violet                                    280                         ruby                                              281                         red                                               282                         blue                                              ______________________________________                                    

TABLE 15

Coupling component: ##SPC35##

    No.     Diazo component       Hue                                             ______________________________________                                        283                           red                                             284                           red                                             285                           ruby                                            286                           red                                             ______________________________________                                    

Other valuable dyes are described in the following Tables:

                                      Table 16                                    __________________________________________________________________________    No.                                                                              Dye                                             Hue                        __________________________________________________________________________    287                                                scarlet                    288                                                violet                     289                                                violet                     290                                                orange                     291                                                violet                     __________________________________________________________________________

TABLE 17 ##SPC36##

    No.                                                                              R   X               Y               Hue                                    __________________________________________________________________________    292                                                                              --CH.sub.3                                                                        --CO.sub.2 CH.sub.3                                                                           --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       bluish red                             293                                                                              --CH.sub.3                                                                        --COCH.sub.3    --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       "                                      294                                                                              --CH.sub.3                                                                        --COCH.sub.3    --(CH.sub.2).sub.3 --O--CH.sub.2 --C.sub.6                                                    ".sub.5                                295                                                                              --CH.sub.3                                                                        --COCH.sub.3    --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub                           .6 H.sub.5      "                                      296                                                                              --CH.sub.3                                                                        --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       --COCH.sub.3    "                                      297                                                                              --CH.sub.3                                                                        --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub.6 H.sub.5                                 --COCH.sub.3    "                                      298                                                                              --CH.sub.3                                                                        --CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                           --SO.sub.2 CH.sub.3                                                                           "                                      299                                                                              --CH.sub.3                                                                        --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub.6 H.sub.5                                 --SO.sub. 2 CH.sub.3                                                                          "                                      300                                                                              --CH.sub.3                                                                        --SO.sub.2 CH.sub.3                                                                           --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4 --OH                                                 "                                      301                                                                              --CH.sub.3                                                                        --SO.sub.2 CH.sub.3                                                                           --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       "                                      302                                                                              --CH.sub.3                                                                        --SO.sub.2 --C.sub.6 H.sub.5                                                                  --(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2 --OH                                                 "                                      __________________________________________________________________________

TABLE 18 ##SPC37##

    No.                                                                              R   X               Y               Hue                                    __________________________________________________________________________    303                                                                              --CH.sub.3                                                                        --COCH.sub.3    --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4 --OH                                                 reddish orange                         304                                                                              H   "               --(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2 --OH                                                 "                                      305                                                                              H   "               --(CH.sub.2).sub.3 --O--COCH.sub.3                                                            "                                      306                                                                              H   "               --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       "                                      307                                                                              H   "               --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub                           .6 H.sub.5      "                                      308                                                                              H   "               --(CH.sub.2).sub.3 --O--CH.sub.2 --C.sub.6                                                    ".sub.5                                309                                                                              CH.sub.3                                                                          --CH.sub.2 --CH.sub.2 --CH.sub.2 --OCOCH.sub.3                                                --COCH.sub.3    orange                                 310                                                                              CH.sub.3                                                                          --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       "               "                                      311                                                                              CH.sub.3                                                                          --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub.6 H.sub.5                                 "               "                                      312                                                                              CH.sub.3                                                                          "               --CHO           "                                      313                                                                              CH.sub.3                                                                          --CH.sub.2 --CH.sub.2 --OCH.sub.3                                                             --COCH.sub.2 --O--C.sub.6 H.sub.5                                                             "                                      314                                                                              CH.sub.3                                                                          --COC.sub.6 H.sub.5                                                                           --(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2 --OH                                                 scarlet                                315                                                                              CH.sub.3                                                                          --COCH=CH--C.sub.6 H.sub.5                                                                    --CH.sub.2 --CH.sub.2 OCH.sub.3                                                               orange                                 316                                                                              CH.sub.3                                                                          --SO.sub.2 CH.sub.3                                                                           --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.4 --OH                                                 reddish orange                         317                                                                              CH.sub.3                                                                          --SO.sub.2 C.sub.2 H.sub.5                                                                    "               "                                      318                                                                              CH.sub.3                                                                          --SO.sub.2 C.sub.6 H.sub.5                                                                    --(CH.sub.2).sub.2 --O--(CH.sub.2).sub.2 --OH                                                 "                                      319                                                                              CH.sub.3                                                                          --SO.sub.2 CH.sub.3                                                                           --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       "                                      320                                                                              CH.sub.3                                                                          "               --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub                           .6 H.sub.5      "                                      321                                                                              H   "               --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       "                                      322                                                                              H   "               --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub                           .6 H.sub.5      "                                      323                                                                              H   --(CH.sub.2).sub.3 --O--(CH.sub.2).sub.2 --O--C.sub.6 H.sub.5                                 --SO.sub.2 H.sub.3                                                                            orange                                 324                                                                              CH.sub.3                                                                          "               "               "                                      325                                                                              CH.sub.3                                                                          --CH.sub.2 --CH.sub.2 --C.sub.6 H.sub.5                                                       "               "                                      __________________________________________________________________________

We claim:
 1. A dye of the formula ##SPC38##where D is phenyl substitutedby chlorine, bromine, methyl, methoxy, nitro, cyano, methylsulfonyl,ethylsulfonyl, phenylsulfonyl, carbalkoxy of a total of 2 to 5 carbonatoms, carbo-β-alkoxyethoxy, said alkoxy having 1 to 4 carbon atoms, orN,N-dialkyl-substituted sulfamoyl, said alkyl having 1 to 3 carbonatoms; phenylazophenyl; phenylazophenyl substituted by chlorine, bromineor nitro; benzthiazolyl; benzthiazolyl substituted by nitro, cyano,methylsulfonyl or ethylsulfonyl; benzisothiazolyl substituted bychlorine, bromine, cyano or nitro; thiazolyl substituted by cyano ornitro; thienyl substituted by methyl, cyano, nitro or carbalkoxy of atotal of 2 to 5 carbon atoms; or thiadiazolyl substituted by phenyl,methyl, chlorine, bromine, methylmercapto, ethylmercapto oralkoxycarbonylethylmercapto, said alkoxy having 1 to 4 carbon atoms; andone of the radicals X and Y is alkanoyl of 1 to 8 carbon atoms, benzoyl,NC--CH₂ CO--, ClCH₂ CO--, H₅ C₆ CH₂ CO--, H₅ C₆ OCH₂ CO--, --SO₂ CH₃,--SO₂ C₂ H₅ or SO₂ C₆ H₅ and the other hydrogen; alkyl of 1 to 6 carbonatoms; alkyl of 2 to 6 carbon atoms substituted by hydroxy, cyano,methoxy, ethoxy, phenoxy, phenoxyethoxy, benzyloxy or phenyl;cyclohexyl; norbornyl: phenyl; β-hydroxy-β-phenylethyl; or (CH₂)₃ (OC₂H₄)_(n) OR, R being alkyl of 1 to 4 carbon atoms or benzyl and n beingthe integer 1 or
 2. 2. A dye as claimed in claim 1 of the formula##SPC39##where A is nitro, cyano, chloro, bromo, carbomethoxy,carbethoxy, β-methoxycarbethoxy, methylsulfonyl, ethylsulfonyl, methyl,methoxy or phenylazo; A¹ is hydrogen, nitro, chloro, bromo, cyano,methyl, methoxy, carbomethoxy, carbethoxy, methylsulfonyl orethylsulfonyl; A² is hydrogen, chloro, bromo, cyano, methyl, methoxy,carbomethoxy or carbethoxy; and X and Y have the meanings given in claim1.